Process for the manufacture of a 1,2-epoxide and a device for carrying out said process

ABSTRACT

Apparatus and processes are provided for forming epoxide compounds. In one embodiment, a process for the manufacture of an epoxide is provided including adding an oxidant, a water-soluble manganese complex and a terminal olefin to form a multiphasic reaction mixture, reacting the terminal olefin with the oxidant in the multiphasic reaction mixture having at least one organic phase in the presence of the water-soluble manganese complex, separating the reaction mixture into the at least one organic phase and an aqueous phase, and reusing at least part of the aqueous phase. The invention is also related to a device for performing the above process.

RELATED APPLICATION DATA

This application claims the benefit of PCT Application PCT/EP2011/000320with an International Filing Date of Jan. 26, 2011, published as WO2011/107188, which PCT Application PCT/EP2011/000320 further claimspriority to European Patent Application No. EP10001035.4 filed Feb. 2,2010, the entire contents of both applications are hereby incorporatedby reference.

FIELD OF INVENTION

The invention relates to the manufacture of a 1,2-epoxide in thepresence of a water-soluble manganese complex as an oxidation catalystand to a device for carrying out said process.

BACKGROUND OF INVENTION

A process for the manufacture of a 1,2-epoxide is described in thepublished European patent application EP 2149569. It describes thecatalytic oxidation of a terminal olefin using a water soluble manganesecomplex as the oxidation catalyst.

The process described is carried out in a multiphasic, e.g. biphasicsystem, i.e. a system comprising an organic phase, which may be a liquidor a gaseous phase, and an aqueous phase. The actual reaction takesplace in the aqueous phase, while the resulting epoxide productseparates from the aqueous phase into the organic phase due to lowsolubility of, or extraction or stripping by the organic phase. For thisreason, the 1,2-epoxide is produced at high turnover numbers (TON), withhigh selectivity towards the 1,2-epoxide with moreover improved ease ofisolating the produced 1,2-epoxide.

Typically the catalyst system used to achieve the above advantagescomprises a manganese atom or a number of manganese atoms coordinatedwith a ligand or ligands. Of particular interest are binuclear manganesecomplexes. As an example of the above manufacture of 1,2-epoxide,reference is made to the European patent application publication EP2149570, which describes the oxidation of allyl chloride to produceepichlorohydrin. EP 2149569 denotes further that the process may becarried out in a reactor, but does not elaborate on this. It turned out,however, that upon isolation of the 1,2-epoxide, an aqueous phase wasleft which comprised an active catalyst fraction. EP 2149569 does notdescribe any further use for this fraction, meaning that part of thecatalyst is wasted, which is not efficient. Another example about amanufacturing method of propylene oxide is presented in thenon-published European patent application 09075528.

DISCLOSURE OF THE INVENTION

It is therefore an object of the current invention to provide a processwith improved catalyst efficiency.

It is another object of the invention to provide a process with improvedselectivity towards the product.

It is yet another object of the invention to provide a process with lowenergy requirements for separation and purification steps.

It is still another object of this invention to provide a device, e.g. areactor, to may out the manufacture of the 1,2-epoxide.

Yet another object if this invention is to provide a reactor which is assmall as possible while having the same improved productivity perreactor volume.

One or more of the above objects are achieved by a process for themanufacture of an epoxide, including adding an oxidant, a water-solublemanganese complex, and a terminal olefin to form a multiphasic reactionmixture, wherein the water-soluble manganese complex is a mononuclearspecies of the general formula (I): [LMnX₃]Y (I), or a binuclear speciesof the general formula (II): [LMn(μ−X)₃MnL](Y)_(n) (II), wherein Mn is amanganese; L or each L independently is a polydentate ligand, each Xindependently is a coordinating species and each μ−X independently is abridging coordinating species, and wherein Y is a non-coordinatingcounter ion, reacting the terminal olefin with, the oxidant in themultiphasic reaction mixture having at least one organic phase in thepresence of the water-soluble manganese complex, separating the reactionmixture into the at least one organic phase and an aqueous phase, andreusing at least part of the aqueous phase.

DETAILED DESCRIPTION OF THE FIGURE

The following is a brief description of figures wherein like numberingindicates like elements.

FIG. 1, illustrates a schematic representation of an embodiment of adevice for the manufacture of epichlorohydrin.

MODE(S) FOR CARRYING OUT THE INVENTION

The invention is based on the observation that the separated aqueousphase contains catalyst which is still active. This has led the currentinventors to the insight that reusing at least part of the separatedaqueous phase comprising the catalyst, leads to a more efficient use ofthe catalyst, and lower energy consumption in subsequent separatingsteps. The combination of a well dispersed biphasic reaction system andreuse of the aqueous phase may lead to a high turn over number, (TON),which is the number of moles of terminal olefin a mole of catalyst canconvert before becoming inactivated. Said combination may further leadto a minimized energy consumption for subsequent separation andpurification steps, high selectivity towards product for all rawmaterials and effective usage of reactor volume leading to a lesscomplicated process. The invention is hereafter discussed in greaterdetail.

The process is carried out in a multiphasic system of an aqueous phaseand at least one organic phase. The oxidation (step a)) of the terminalolefin is believed to take place in an aqueous phase, whereas theorganic phase is believed to extract or strip produced 1,2-epoxide fromthe water phase. The inventors have found that the organic phasecontains little or no water soluble byproducts and catalyst. It isbeneficial to use a terminal olefin which has limited solubility inwater, for example, allyl chloride and allyl acetate instead ofconventionally used allyl alcohol. The multiphasic system may be createdby adding the terminal olefin with limited solubility to an aqueousphase in an amount greater than what dissolves in the aqueous phase.Preferred terminal olefins have a maximum solubility of about 100 g/L(at 20° C.), more preferably of from 0.01 to 100 g/L.

The volumetric ratio of the organic phase to the aqueous phase, bothinside the reactor, and the degree of contact between the phases areimportant parameters in the performance of the catalyst system. If theamount of organic phase is too high, the aqueous phase is no longer thecontinuous phase. In this case, there may be insufficient mixing of theingredients. This means that the conversion rate of terminal olefin isconsiderably lowered. On the other hand, if the aqueous phase inside thereactor is too high with respect to the amount of organic phase, theterminal olefin concentration in the aqueous phase will be too low withrespect to oxidant concentration. This may lead to the production ofundesirable side products and catalyst deactivation. Therefore thevolumetric ratio of aqueous phase to organic phase inside the reactor ispreferably in the range of from 10:1 to 1:5, with emulsion formation asa maximum limit.

The above limitations can also be influenced by the degree of mixing. Inpractice this means that the organic phase needs to be well dispersedinto the continuous aqueous phase, such as in the form of droplets,preferably as small as possible, for example, less than 3 mm.

Upon dispersion of the organic phase into the aqueous phase, thereaction (catalytic oxidation) of the terminal olefin and the oxidant inthe presence of the catalyst may occur (step a)). The resulting reactionmixture is discharged from the reactor. The discharged reaction mixturecomprises both product and unreacted starting material. The dischargedreaction mixture is allowed to settle into its separate phases, theaqueous phase and the at least one organic phase. The at least oneorganic phase may comprise two organic phases, such as one dispose belowand one disposed above the aqueous phase.

The current inventors surprisingly found that the aqueous phase containscatalyst which is still active. The catalyst contained within theseparated aqueous phase, can be reused, thereby increasing the catalystefficiency.

It is believed to be beneficial that the aqueous phase contains at leasttrace amounts of the terminal olefin. Without being bound to any theory,it is believed that the presence of terminal olefin allows the catalystto remain active, whereas it is believed that without the presence ofterminal olefin and/or due to the presence of the epoxide and/or oxidantwithout terminal olefin present the activity of the active catalystreduces. Cooling may also be used to reduce the decrease in catalystefficiency.

The aqueous phase can be reused by feeding at least a portion (part) ofthe separated aqueous phase to a next reactor or by recycling at least aportion of the separated aqueous phase to the same reactor (step d)).Preferably, the at least a portion of the aqueous phase is recycled intothe reaction mixture. This way, catalyst present in the recycled aqueousphase is not discharged, but efficiently used again.

When the process is running, per unit time, certain volumes of aqueousstarting materials, such as the oxidant, catalyst and, if needed,buffer, are supplied to the reaction mixture (step a)).

These aqueous starting materials are indicated as the aqueouscomponents. Simultaneously, per unit time, also a certain volume ofseparated aqueous phase is recycled into the reaction mixture. The massratio of the volume of aqueous components to the volume of recycledaqueous phase added to the reaction mixture at every instant isindicated as the water recycle ratio. In order to achieve theadvantageous effects of recycling the catalyst, said water recycle ratiopreferably is in the range of from 10:1 to 1:10, more preferably of from2:1 to 1:5 and most preferably 1:3.5. Also, turbulent conditions such asa high velocity of the aqueous phase will prevent agglomeration of theorganic droplets dispersed in said medium.

The molar ratio of terminal olefin to oxidant is very important in theprocess of the current invention. The molar ratio of terminal olefin tooxidant may be greater than 1:2. Preferably, this ratio is in the rangeof from 12:1 to 1:1. More preferably, this ratio may be 1:1, 1.2:1, 2:1,or 4:1, or 2:1 to 12:1. If too much oxidant is used, then theselectivity towards the 1,2-epoxide reduces due to the production ofundesirable side-products. Another consequence of too much oxidant withrespect to terminal olefin is rapid catalyst deactivation. If not enoughoxidant is used, then the turnover number is suboptimal. This istherefore significantly different from bleaching conditions described inthe prior art, where excessive amounts of oxidant, i.e. hydrogenperoxide are used. To ensure optimal peroxide efficiency, the oxidant ispreferably added to the aqueous phase at a rate about equal to thereaction rate of the catalytic oxidation.

The reaction (catalytic oxidation) is carried out using hydrogenperoxide, or a precursor thereof, as an oxidant. Hydrogen peroxide hasstrong oxidizing properties. It is typically used in an aqueoussolution. The concentration of hydrogen peroxide may vary, from 15%(e.g., consumer grade for bleaching hair) to 98% (propellant grade),with a preference for industrial grades varying from 30 to 70%. Morepreferably, the concentration of hydrogen peroxide is 70%. Otheroxidants that may be used include organic peroxides, peracids, andcombinations thereof.

The reaction (catalytic oxidation) of the terminal olefin takes place inthe aqueous phase. The aqueous phase may have a pH from 1 to 8, such asfrom 2 to 5. The aqueous phase may further comprise a buffer system tostabilize the pH in a certain range. For instance, it has been foundadvantageous that the aqueous phase is stabilized in a pH range of from1 to 8, more preferably of from 2 to 5. The pH is therefore (well) belowthat used when bleaching olefins with hydrogen peroxide as the oxidant,typically carried out at more alkaline conditions (e.g., pH adjustedwith NaHCO₃ to 9.0). The suitable or preferred range may be achieved byseveral known acid-salt combinations, with the preferred combinationbeing based on oxalic acid-oxalate salt, acetic acid-acetate salt,malonic acid-malonate salt, and combinations thereof.

The aqueous phase may further comprise minor amounts, if any, of otherorganic compounds. The aqueous phase may also contain minor amounts ofco-solvents, e.g. to increase the solubility of the olefin. Suitableco-solvents include, for example, acetone, methanol, and otherwater-soluble alcohols. Co-solvents may be used in amounts such as tokeep a biphasic system, preferably in an amount <10 weight percent.

The aqueous phase may further comprise a phase transfer agent and/or asurfactant, in particular if a terminal olefin is used with lowsolubility (e.g., below 0.1 g/L water). Known phase transfer agents thatmay be used in the process of the invention include quaternary alkylammonium salts. Known surfactants that may be used in the process of theinvention include non ionic surfactants such as Triton X100™ availablefrom Union Carbide.

The catalyst system comprising a water soluble manganese complex isdescribed as follows. The oxidation catalyst is a water solublemanganese complex. Advantageously, the manganese complexes includemononuclear species of the general formula (I):[LMnX₃]Y  (I),and binuclear species of the general formula (II):[LMn(μ−X)₃MnL](Y)_(n)  (II),wherein Mn is a manganese; L or each L independently is a polydentateligand, preferably a cyclic or acyclic compound containing 3 nitrogenatoms; each X is independently a coordinating species and each μ−X isindependently a bridging coordinating species, selected from the groupconsisting of: RO⁻, Cl⁻, Br⁻, I⁻, F⁻, NCS⁻, N₃ ⁻, I₃ ⁻, NH₃, NR₃, RCOO⁻,RSO₃ ⁻, RSO₄ ⁻, OH⁻, O²⁻, O₂ ²⁻, HOO⁻, H₂O, SH⁻, CN⁻, OCN⁻, and S₄ ²⁻and combinations thereof, wherein R is a C₁-C₂₀ radical selected fromthe group consisting of alkyl, cycloalkyl, aryl, benzyl and combinationsthereof, and Y is a non-coordinating counter ion selected from the groupconsisting of RO⁻, Cl⁻, Br⁻, I⁻, F⁻, SO₄ ²⁻, RCOO⁻, PF₆ ⁻, acetate,tosylate, triflate (CF₃SO₃ ⁻) and a combination thereof with R onceagain being a C₁ to C₂₀ radical selected from the group consisting ofalkyl, cycloalkyl, aryl, benzyl and combination thereof. Thenon-coordinating counter ion Y may provide for the charge neutrality ofthe complex and the value of n depends upon the charge of the cationiccomplex and anionic counter ion Y, for example, n may be 1 or 2. In oneembodiment, an ion of CH₃COO⁻ or PF₆ ⁻ may be used as thenon-coordinating counter ion. Ligands which are suitable for the presentinvention are acyclic compounds containing at least 7 atoms in thebackbone or cyclic compounds containing at least 9 atoms in the ring,each having the nitrogen atoms separated by at least two carbon atoms. Apreferred class of ligands is that based on (substituted)triazacyclononane (“Tacn”). The preferred ligand is1,4,7-trimethyl-1,4,7,-triazacyclononane (“TmTacn”).

Dinuclear manganese complexes are denoted as preferred, because of theirgreater activity and solubility in water. Preferred dinuclear manganesecomplexes are those of the formula [Mn^(IV) ₂(μ−O)₃L₂](Y)_(n) (same asformula: [LMn(μ−O)₃MnL](Y)_(n)), wherein n is 2, and L and Y have themeaning identified above, preferably TmTacn as ligand, and PF₆ ⁻ oracetate (CH₃CO₂ ⁻, hereinafter OAc) as counterion. The catalyst systemcomprising a water soluble manganese complex is described above. Thepreferred complex for the current invention comprises1,4,7-trimethyl-1,4,7,-triazacyclononane (“TmTacn”) as the preferredligand or ligands. This ligand is commercially available from Aldrich.

The manganese complex is used in catalytically effective amounts.Typically, the catalyst is used in a molar ratio of catalyst (Mn) to theoxidant of from 1:10 to 1:10,000,000, preferably of from 1:100 to1:1,000,000, most preferably of from 1:1000 to 1:100,000. As a matter ofconvenience the amount of catalyst may also be expressed in terms of itsconcentration, when keeping in mind the volume of the aqueous medium.For instance, it may be used in a molar concentration (based on the Mn)of from 0.001 to 10 mmol/L, preferred of from 0.01 to 7 mmol/L and mostpreferably of from 0.01 to 2 mmol/L.

The reaction conditions for the catalytic oxidation may be quicklydetermined by a person skilled in the art. The reaction is exothermic,and cooling of the reaction mixture may be required. The reaction ispreferably carried out at temperatures anywhere from −5° C. to 40° C.,dependent upon such physical parameters as melting and boiling point ofthe used terminal olefins.

According to the invention, the terminal olefin used is an epoxidizibleolefin which may be functionalized. The terminal olefin may be a liquidunder process conditions, e.g., allyl chloride or liquefied propylene,but also a gas, e.g. gaseous propylene.

Examples of suitable terminal olefins include terminal olefinicallyunsaturated compounds. In one embodiment, the terminal olefinicallyunsaturated compound may have at least one unsaturated —C═C— bond, suchas at least one unsaturated —C═CH₂ group. The olefinically unsaturatedcompound may comprise more than one unsaturated —C═C— bond. Moreover,the unsaturated —C═C— bond need not be a terminal group. Terminallyolefinically unsaturated compounds may have one or more terminal —C═CH₂bonds.

Suitable examples of terminal olefinically unsaturated compoundstherefore include the following compounds:R—CH═CH₂R′—(CH═CH₂)_(n)X—CH═CH₂Y—(CH═CH₂)₂wherein R is a radical of 1 or more carbon atoms optionally comprising 1or more heteroatoms (such as oxygen, nitrogen or silicon); R′ is amultivalent radical of 1 or more carbon atoms optionally comprising 1 ormore heteroatoms wherein n corresponds with the valence of themultivalent radical; X is a halogen atom, and Y is an oxygen atom.

Of particular interest are olefinically unsaturated compounds selectedfrom the compounds:

(a) vinylchloride or allylchloride;

(b) 1-alkene, preferably propene:

(c) mono-, di- or polyallyl ethers of mono-, di- or polyols;

(d) mono-, di- or polyvinyl ethers of mono-, di- or polyols;

(e) mono-, di- or polyallyl esters of mono-, di- or polyacid;

(f) mono-, di- or polyvinyl esters of mono-, di- or polyacids;

(g) divinylether or diallylether.

The terminal olefin may have limited solubility in water, for example,the terminal olefin may have a maximum solubility in the aqueous phaseat 20° C. of about 100 g/L, more preferably of from 0.01 to 100 g/L at20° C.

In a more preferred embodiment of the present invention, the terminalolefin is selected from allyl bromide, allyl chloride and allyl acetate.In a most preferred embodiment of the invention allyl chloride is usedfor the manufacture of epichlorohydrin, because of the commercialinterest and ease of isolating the produced epichlorohydrin.

According to another preferred embodiment of the present invention theterminal olefin is propylene in order to produce propylene oxide, andthe reaction is carried out at temperatures in the range from −5° C. to40° C. Propylene is preferably used in excess over the oxidant.

According to still another embodiment of the invention, the buffer, ifany, and oxidation catalyst are fed as a pre-mixed mixture into step a).

Another aspect of the invention is related to a device carrying out theabove process for the manufacture of 1,2-epoxide. According to theinvention, the device comprises a reactor for performing the catalyticoxidation having an inlet for feeding the oxidant, the oxidationcatalyst, optionally a buffer and the terminal olefin to the reactor,and an outlet for discharging the reaction mixture from said reactor,separating means connected to the reactor outlet for separating thereaction mixture into the at least one organic phase and an aqueousphase, recycling means for recycling part of the aqueous phase separatedin the separating means, dispersing means for dispersing the terminalolefin into the aqueous phase and cooling means for controlling thetemperature of the catalytic oxidation process.

According to the invention, the device comprises a reactor for carryingout the process having an inlet and an outlet. Via the reactor inlet thereactants are fed to the reactor, whereas via the reactor outlet thereaction mixture is discharged. The device farther comprises separatingmeans connected to the reactor outlet for separating the reactionmixture into the at least one organic phase and the aqueous phase asexplained above. Preferably, this separation means comprises a straightforward liquid to liquid separator, such as a settling tank, since theproduct forms at least one separate organic phase which phase separatesfrom the aqueous phase when allowed to settle. Other devices such ashydrocyclones can also be used.

The aqueous phase is recycled into the reactor via the inlet of thereactor. This recycling means may be of simple design, e.g. a pipeconnecting an aqueous phase outlet of the separation means and thereactor inlet equipped with a pump to transport the aqueous phase intothe reactor. It is noted here that the skilled person will be aware thatthe reactor according to the invention is equipped with standard processtechnological elements like e.g. pumps, valves and control mechanisms.

The reactor according to the invention further comprises dispersingmeans for dispersing the organic terminal olefin phase into the aqueousphase and cooling means for controlling the temperature of the catalyticoxidation, because of its exothermic nature.

About the reactor type, several reactor designs are suited to carry outthe process according to the invention. The reactor may be a plug flowreactor (PFR). Due to the required high velocity for dispersing and thelong residence times a PFR used in the present invention will be a verylong PFR. The reactor may also be a continuous stirred tank reactor(CSTR). When using a CSTR, special care should be taken in dispersingthe terminal olefin into the aqueous phase.

According to a preferred embodiment of the invention, the catalyticoxidation may also be carried out in a loop reactor. In a loop reactor,the reaction mixture is circulated. When the circulation rate of theloop reactor is about 15 times the rate at which the aqueous componentsand the terminal olefin is fed, i.e. the feed rate, the loop reactor canbe described as a CSTR because of the high degree of back mixing. Theadvantage of using a loop reactor in the present process is that itallows for the well defined mixing behaviour of a pumped system combinedwith dispersing means in a compact reactor design.

According to yet another preferred embodiment of the invention thedispersing means is a static mixer, since this mixer will providemaximum break up of organic droplets in the continuous aqueous phase.

According to another embodiment of the invention fresh oxidant andolefin are fed to the aqueous phase in subdivided portions to thereactor through multiple inlet parts distributed over the reactorhousing.

The present invention is further explained by means of FIG. 1, whichshows a schematic representation of an embodiment of a device for themanufacture of epichlorohydrin.

It is noted here that the skilled person facing the task of constructingthe device for carrying out the process according to the invention, willbe aware that all process technological elements of the device areconstructed and operated by using common general process technologicalknowledge.

In this embodiment, the device 10 comprises a loop reactor 20 comprisingan inlet 21 and an outlet 22. Hydrogen peroxide, a water solublemanganese complex as the oxidation catalyst, an oxalate buffer solutionand allyl chloride, which are disposed in separate feeding tanks 15, arefed to the reactor 20. The reactants are transported from the feedingtanks 15 to the reactor inlet 21 through feeding conduits 11 by means offeeding pumps 12. A pre-mixing means 50 may be disposed between theinlet 21 and one or more of the feeding pumps 12 to pre-mix some of thecomponents, such as the catalyst and oxalate buffer in FIG. 1. Thereactor inlet 21 advantageously comprises several inlet ports, one portfor each reactant. The reaction mixture is discharged from the reactor20 via the reactor outlet 22 into a separating means 30. The reactoroutlet 22 and separating means 30 are connected via a discharge conduit13. The separating means 30 comprises a separation inlet 31 throughwhich the reaction mixture is supplied to the separating means 30. Inthe separating means 30 the at least one organic phase and the aqueousphase are allowed to phase separate. The organic phase comprisingepichlorohydrin is isolated from the separating means 30 through theproduct outlet 32.

At least part of the aqueous phase in the separating means 30 isrecycled to the reactor 20 via a recycling conduit 41 connecting arecycling outlet 33 of separating means 30 and reactor inlet 21. Arecycling pump 42 is comprised in the recycling conduit 41 to transportthe aqueous phase. The organic phase inside the reactor 20 is dispersedin the aqueous phase using a dispersing means 23. The reactor 20 furthercomprises a reactor pump 26 for transporting the reaction mixture andcooling means 24 to cool the reaction mixture. Said cooling means 24 maybe e.g. a water cooler or other types of heat exchanging means. However,the choice of the type of cooling means 24 is left to the expertise ofthe skilled person.

What is claimed is:
 1. A process for the manufacture of an epoxide,comprising: a) adding an oxidant, a water-soluble manganese complex, anda terminal olefin to form a multiphasic reaction mixture comprising atleast one organic phase and an aqueous phase, wherein the water-solublemanganese complex is a mononuclear species of the general formula (I):[LMnX₃]Y  (I)  or a binuclear species of the general formula (II):[LMn(μ−X)₃MnL](Y)_(n)  (II)  wherein Mn is a manganese; L or each Lindependently is a polydentate ligand, each X independently is acoordinating species and each μ−X independently is a bridgingcoordinating species, and wherein Y is a non-coordinating counter ion;b) reacting the terminal olefin with the oxidant in the multiphasicreaction mixture having at least one organic phase in the presence ofthe water-soluble manganese complex; c) separating the at least oneorganic phase and the aqueous phase, wherein the aqueous phase comprisesthe water-soluble manganese complex; and d) reusing at least part of theaqueous phase.
 2. The process according to claim 1, wherein step a)comprises the sub steps of: a1) adding to the reaction mixture theoxidant and the water-soluble manganese complex as aqueous phasecomponents; and a2) dispersing the terminal olefin into the aqueousphase.
 3. The process of claim 1, wherein the reaction takes place in anaqueous phase of the multiphasic reaction mixture.
 4. The process ofclaim 1, wherein the reusing at least part of the aqueous phasecomprises at least a portion of the aqueous phase obtained in step c) isrecycled into step a).
 5. The process of claim 2, wherein the waterrecycle ratio of aqueous components to reused aqueous phase is in therange of from 10:1 to 1:10.
 6. The process according to claim 5, whereinthe water recycle ratio is about 1:3.5.
 7. The process of claim 1,wherein the molar ratio of terminal olefin to oxidant is in the range offrom 12:1 to 1:1.
 8. The process of claim 1, wherein the terminal olefinhas a maximum solubility at 20° C. of about 100 g/L.
 9. The process ofclaim 1, wherein the aqueous phase further comprises a buffer system anda pH in the range of from 1 to 8, and the buffer is added to thereaction mixture as an aqueous component.
 10. The process of claim 1,wherein the reaction is carried out at temperatures in the range of from−5° C. to 40° C.
 11. The process of claim 1, wherein the terminal olefinis selected from allyl bromide, allyl chloride and allyl acetate and thereaction is carried out at temperatures in the range from −5° C. to 40°C.
 12. The process of claim 1, wherein the terminal olefin is propyleneand the reaction is carried out at temperatures in the range from −5° C.to 40° C.
 13. The process of claim 1, wherein the molar ratio ofwater-soluble manganese complex to oxidant is in the range of from 1:10to 1:10,000,000.
 14. The process of claim 1, wherein the oxidant ishydrogen peroxide or a precursor thereof.
 15. The process of claim 1,wherein the aqueous phase comprises a pH in the range of from 1 to 5.16. The process of claim 1, wherein each X is independently selectedfrom the group consisting of: RO⁻, Cl⁻, Br⁻, I⁻, F⁻, NCS⁻, N₃ ⁻, I₃ ⁻,NH₃, NR₃, RCOO⁻, RSO₃ ⁻, RSO₄ ⁻, OH⁻, O²⁻, O₂ ²⁻, HOO⁻, H₂O, SH⁻, CN⁻,OCN⁻, and S₄ ²⁻ and combinations thereof, and R is selected from thegroup consisting of C₁-C₂₀ alkyl, C₁-C₂₀ cycloalkyl, C₁-C₂₀ aryl, benzyland combinations thereof.
 17. The process of claim 1, wherein each μ−Xis independently selected from the group consisting of: RO⁻, Cl⁻, Br⁻,I⁻, F⁻, NCS⁻, N₃ ⁻, I₃ ⁻, NH₃, NR₃, RCOO⁻, RSO₃ ⁻, RSO₄ ⁻, OH⁻, O²⁻, O₂²⁻, HOO⁻, H₂O, SH⁻, CN⁻, OCN⁻, and S₄ ²⁻ and combinations thereof, and Ris selected from the group consisting of C₁-C₂₀ alkyl, C₁-C₂₀cycloalkyl, C₁-C₂₀ aryl, benzyl and combinations thereof.
 18. Theprocess of claim 1, wherein Y is a non-coordinating counter ion selectedfrom the group consisting of RO⁻, Cl⁻, Br⁻, I⁻, F⁻, SO₄ ²⁻, RCOO⁻, PF₆⁻, acetate, tosylate, triflate, and a combination thereof, and R isselected from the group consisting of C₁-C₂₀ alkyl, C₁-C₂₀ cycloalkyl,C₁-C₂₀ aryl, benzyl and combination thereof.